2-hydroxy-3-chloroalkyl ethers of acetylenic alcohols



Unite St es 2-HYDROXY-3-CHLOROALKYL ETHERS F ACETYLENIC ALCOHOLS RogerF. Monroe and Arthur W. Anderson, Midland,

Mich, assignors to The Dow Chemical Company, Midland, Mich., acorporation of Delaware No Drawing. Filed Mar. '3, 1958, Ser. No.718,473

5 Claims. (Cl. 260-611) The present invention relates to2-hydroxy-3-chloroalkyl ethers of acetylenic alcohols and is moreparticularly concerned with a new and novel class of compounds whichconveniently may be characterized by the general formulaHCEC-R-O-CHz-(RH-CH:

wherein R represents a bivalent saturated hydrocarbon radical containingfrom 1 to 8 carbon atoms, inclusive six of which may be joined togetherto form a ring. The compounds of the present invention have been testedatent O 2,946,825 Patented July 26, 1960 In the manner of Example 2,1375 parts by weight (14.9 moles) of epichlorohydrin was slowly added to1700 parts by weight (13.5 moles) of 3,5-dimethyl-1-hexyn-3-olcontaining 10 parts by weight of anhydrous stannic chloride and thetemperature maintained between 50 C. and

v 65 C. by external cooling. Upon completion of the reaction, thereaction mixture was washed with water and fractionally distilled underreduced pressure to obtain a 1-chloro-3-(l-isobutyl-l-methylpropynyloxy) -2-propanol product boiling at 78 C. at0.6 mm.

Example 4 In the manner of Example 2 employing 1900 parts by weight (34moles) of propargyl alcohol in place of 3- methyl-l-butynol there wasobtained a 1-chloro-3-propynyloxy-3-propanol product.

It is thus apparent that substantially any acetylem'c alcohol may beemployed in accordance with the present and found to be useful as theactive toxic ingredient in v compositions employed for the control ofseeds and seedlings of undesired vegetation. These compounds are alsouseful as corrosion inhibitors and as intermediates in the preparationof the epoxy ethers of acetylenic alcohols of our concurrently filedapplication Serial No. 718,470. These latter compounds are also usefulas herbicides and as corrosion inhibitors.

The compounds of the present invention conveniently may be prepared byreacting epichlorohydrin and an acetylenic alcohol in the presence of ametallic chloride catalyst. Good results are obtained when employing atleast equimolar proportions of the reactants and preferably whenemploying a molar excess of the alcohol. The reaction proceeds readilyand smoothly at temperatures of from to 80 C.

In accordance with the present invention the new compounds can beprepared by reacting epichlorohydrin with about a molar proportion, andpreferably with up to a 30 percent excess, of the acetylenic alcohol. 7The reaction is somewhat exothermic and external cooling is oftennecessary to maintain the temperature below about 80 C. Upon completionof the reaction the desired product can be obtained by conventionalmethods such as fractional distillation under reduced pressure.

The following examples are illustrative of the present invention but arenot to be construed as limiting.

Example 1 1375 parts by weight (14.9 moles) of epichlorohydrin wereslowly added with stirring to 1680 parts by weight (20 moles) of2-rnethyl-3-butyn-2-ol containing 10 parts by weight of anhydrousstannic chloride. The temperainvention. Some of the more commonacetylenic alcohols in addition to those shown in the examples which aremeant to be within the scope of the present invention g 7 are,forexample, 3-butyn-l-ol, 4-pentyn-1-ol, 2-hexyn-1- ol, S-heptyn-l-ol,and the like.

vegetation. For such use the compounds may be dispersed on a finelydivided carrier and employed as dusts.

The new compounds may also be employed in oils, or

as constituents in water emulsions or water dispersions with or withouta wetting, dispering or emulsifying agent. In a representativeoperation, controls of Phalaris canariensis was obtained with aqueouscompositions containing 100 parts by weight of1-chloro-3-(l-isobutyl-lmethyl-Z-propynyloxy)-2-propanol per millionparts by weight of ultimate mixture.

The compounds of the present invention are also useful as corrosioninhibitors in halogenated hydrocarbon solvent systems. Further thecompounds are useful in preparing the 2,3-epoxypropyl ethers ofacetylenic alcohols of our copending application Serial No. 718,470filed even date herewith. The latter compounds are useful as herbicides.

We claim:

1. A 2-hydroxy-3-chloropropyl ether of an acetylenic alcohol having theformula wherein R is a bivalent saturated hydrocarbon radical havingfrom 1 to 8 carbon atoms, inclusive six of which may be joined togetherto form a ring.

2. 1-chloro-3-( l-ethynylcyclohexyloxy) -2-propanol.

3 1-chloro-3-( l, l-dirnethylpropynyloxy) -2-propano1.

4. lchloro-3-( l-isobutyl-l-methylpropynyloxy)-2 propanel.

5. 1-chloro-3-propargyl0xy-2 propanol.

References Cited in the file of this patent UNITED STATES PATENTS

